AC Ketoxime carbamates

ABSTRACT

Carbamate derivatives of ketoximes are useful in combatting pests such as insects, mites, and nematodes.

O United States Patent 1191 1111 3,875 ,232 Magee Apr. 1, 1975 ACKETOXIME CARBAMATES [58] Field of Search 260/566 AC 75 I t: Th A.M M t.Oh' nven or omas agee, en or 10 e ces Cited [73] Assignee: DiamondShamrock Corporation, UNITED STATES PATENTS Cleveland, Ohio 3,217,03711/1965 Payne et a1 260/566 AC [22] Filed: Feb. 24, 1972 3,400,1539/1968 Payne et 21].... 260/566 AC 3,454,642 7/1969 Friedman 1. 260/566AC [21] 229,207 3,647,861 3/1972 Buchanan 260/566 AC x RehtedApplication Data 3,681,386 8/1972 Fridinger et a1 260/566 AC X [63]Continuation-impart of Scr. No. 132,584, April 8, R N PA ENTS ORAPPLICATIONS 1971, abandoned. 1,090,986 11/1967 United Kingdom [52] U.S.Cl 260/566, 260/244, 260/256.4 R, Primary Examiner Leon Zitver 260/343R, 260/349, 260/454, 260/456 A, 260/463, 260/465.4, 260/482 R, 260/566A, 424/244, 424/246, 424/248, 424/251, 424/272, 424/273, 424/275,424/276, 424/278, 424/300, 424/302, 424/303, 424/304, 424/311, 424/327Int. Cl. C07c 131/00 Assistant Examine'rGera1d A. Schwartz Attorney,Agent, 0r'FirmJohn C. Tiernan; L. G. Nunn [57] ABSTRACT Carbamatederivatives of ketoximes are useful in com batting pests such asinsects, mites, and nematodes.

6 Claims, No Drawings 1 AC KETOXIME CARBAMATES CROSS REFERENCE TORELATED APPLICATION This application is a continuation-in-part ofcopending application. Ser. No. l32,584, Thomas A. Magee, filed Apr. 8,1971 now abandoned.

BACKGROUND OF THE INVENTION 1. Field of the Invention This inventionrelates to organic compounds useful as pesticides and more particularlyto carbamate derivatives of ketoximes having insecticidal, mi'ticidal,and, in some cases, nematocidal activity comparable or superior to themost closely related commercial products while having significantlylower toxicity toward mam mals than these commercial products.

2. Description of the Prior Art The outstanding pesticidal activity ofthe carbamate derivatives of the ketoximes disclosed in this inventionis surprising and unexpected because the prior art indicates thatcarbamate derivatives only of substituted aldoximes have high pesticidalactivity, whereas ketoxime derivatives were essentially inactive. Forexample, U.S. Pat. No. 3,217,037 and US. Pat. No. 3,507,965 showcompounds, possessing pesticidal activity, of the structure:

wherein X O or S(O) when n 0, l, or 2 and the free valances aresatisfied by hydrogen or hydrocarbyl radicals. In these two patents, thepreferred compounds are aldoximes wherein the carbon atom (C attached tothe oxime moiety in the above structure is substituted with hydrogen. Inthe J. Agr. Food Chem., 14, 356 1966), the patentees of these patentsstate, The data... demonstrate...the detrimental effect...of replacingthe aldehydic hydrogen with an alkyl group. All of the ketoximederivatives... were virtually inactive when compared with the aldoximederivative Ketoxime compounds of Formulas (l) and (II) below arereported in the reference as being essentially inactive compared to thealdoxime compound of Formula (Ill) below which is known commercially asaldicarb (Temik). The compound of Formula (II) differs from the compoundof Formula (Ill) only in that a methyl group has been substituted forthe aldehydric hydrogen of Formula (Ill).

0 ll ens QIOCIM'HCIL- cm, s-g-c-ca clh m EOCIHKCEL; cm, s-e --0H Theketoxime derivatives of Formulas (l) and (II) have been resynthesizedand tested and their reported lack of activity relative to that of thecompound of Formula (lll) reconfirmed. Surprisingly, however, theketoxime derivatives of the present invention have been found to possesshigh pesticidal activity, comparable or superior to that of the compoundof Formula (Ill).

SUMMARY OF THE INVENTION The carbamates of ketoximes of the presentinvention can be represented by the formula:

R -R hydrogen, lower alkyl, lower alkenyl. lower alkynyl, substitutedlower alkyl, alkenyl, or alkynyl with the proviso that R and R may beconnected to form a cycloaliphatic ring;

R R -R or X with the proviso that when R, and X are OR SR S(O)R,,, SO.,R,,, or NR,,R,,, R and X may be connected to form a heterocyclic ring;

R -R hydrogen, lower alkyl, lower alkenyl, or

lower alkynyl;

X SR S(O)R,,, SO R,,, OR OSO R NR R N0 CN, SCN, N or halogen;

R hydrogen, lower alkyl, lower alkenyl, lower alkynyl, aryl, substitutedaryl, carbamyl, substituted carbamyl, acyl, or substituted acyl with theproviso that the lower alkyl or alkenyyl groups may be furthersubstituted with X; and

R hydrogen or lower alkyl with the proviso that R R and N in the NR Rgroup may form a heterocyclic ring.

The term lower alkyl radical means a radical having from one to aboutseven carbon atoms.

This invention specifically includes those carbamates of Formula (IV)where R and R are lower alkyl radicals such as methyl; R is either R orX; R and R are hydrogen; X is s( )nRg Where n O, 1, or 2; R is a loweralkyyl radical such as methyl; and R and R are individually hydrogen, alower alkyl radical such as methyl or a lower alkenyl radical.

It is completely unexpected to discover that carbamate derivatives ofketoximes such as the carbamate of Formula (V) have pesticidal activitycomparable to that of the carbamate derivative of the aldoxime ofFormula (Ill):

0 sa oiimica CH3 -('1-C-CH2SCH3 and simultaneously exhibit significantlylower toxicity toward mannals than does the compound of Formula (Ill).Thus, the oral toxicity of the compound of Formula (V), measured onalbino rats and expressed as the LD was found to be 8.5 mgm/kg of bodyweight; the dermal toxicity, measured on albino rabbits, again expressedas the LD was 38.9 mgm/kg of body weight. LD is a standard means ofexpressing toxicity and indicates the concentration required to kill509'! of the test animals. In each case, the LD value is approximatelyeight times greater than the reported value for the carbamate derivativeof the aldoxime compound of Formula (III).

It is an object of this invention to provide carbamates of substitutedketoximes, which are useful pesticides. A further object is to provide amethod for producing these carbamates. Another object is to providepesticidal compositions containing these carbamates. Still anotherobject is to provide methods for combatting pests such as insects,mites, and nematodes using these carbamates. It is intended. however,that the detailed description and specific examples given herein do notlimit this invention but merely indicate preferred embodiments thereofsince various changes and modifications within the scope of thisinvention will become apparent to those skilled in the art.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred compounds of Formula(IV) include carbamate derivatives of l-hydrocarbylthio(or l-azido)-2-alkanone oximes wherein the carbamate nitrogen can be substituted withzero, one, or two lower alkyl groups; the carbon atom (C substituted bythe hydrocarbylthio(or azido) group is not further substituted; and thecarbon atom (C not substituted by the hydrocarbylthio-(or azido) groupsis preferably substituted with an alkyl group and is optimallycompletely alkylated to provide a maximum degree of branching on thiscarbon atom.

A second preferred group of Formula (IV) compounds include carbamatederivatives of lhydrocarbylthio(or l-azido)-2-alkanone oximes whereinthe carbamate nitrogen can be substituted with zero, one, or two loweralkyl groups; the carbon atom (C substituted by the hydrocarbylthio(orazido) group is not further substituted; and the carbon atom (C ispreferably substituted with a substituent of group X and is optimallyfurther completely alkylated to provide a maximum degree of branching onthis carbon atom.

These compounds exhibit extremely high activity as insecticides andmiticides, both as contact and as systemic toxicants. In some cases,they show high nematocidal activity.

As specific examples of these compounds, there may be mentionedl-hydrocarbylthio-3,3-dimethyl-2 methylcarbamylouminobutanes such as:l-methylthio-3,3-dimethyl-2-methylcarbamyloximinobutane;l-ethylthio-3,3-dimethyl-2-methylcarbamyloximinobutane;l-n-propylthio-3,3-dimethyI-Z-methylcarbamyloximinobutane;l-isopropylthio-3,3-dimethyl-2-methylcarbamyloximinobutane;l-n-butylthio-3,3-dimethyl-2-methylcarbamyloximinobutane;l-tert.-butylthio-3,3-dimethyl-Z-methylcarbamyloximinobutane;l-sec.-butylthio-3,3-dimethyl-2methylcarbamyloximinobutane;

4 l-isobutylthio3 ,3-dimethyl-2-methylcarbamyloximinobutane;l-vinylthio-3,3-dimethyl'2-methylcarbamyloximinobutane;l-(Z-propenylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane;l(3-butenylthio)-3,3-dimethyl-Z-methylcarbamyloximinobutane;l-ethynylthio-3,3-dimethyl-2-methylcarbamyloximinobutane;l-phenylthio-3,3-dimethyl-2-methylcarbamyloximinobutane;l-benzylthio-3,3-dimethyl-2-methylcarbamyloximinobutane; and the like;also the analogous l-hydrocarbylthio-3-methyl-2-methylcarbamyloximinobutanes such as:l-methylthio-3-methyl-2-methylcarbamyloximinobutane;l-ethylthio-3-methyl-2-methylcarbamyloximinobutane;l-n-propylthio-3-methyl-Z-methylcarbamyloximinobutane;l-isopropylthio-3-methyl'2-methylcarbamyloximinobutane;l-n-butylthio-3-methyl-2-methylcarbamyloximinobutane;1-tert.-butylthio-3-methyl-2-methylcarbamyloximinobutane;l-sec.-butylthio-3-methyl-2-methylcarbamyloximinobutane;l-isobutylthio-3-methyl-2-methylcarbamyloximinobutane;l-vinylthio-3-methyl-2-methylcarbamyloximinobutane;l-(2-propenylthio)-3-methyl-Z-methylcarbamyloximinobutane; l-(3-butenylthio )-3-methyl-2-methylcarbamyloximinobutane;l-ethynylthio-3-methyl-Z-methylcarbamyloximinobutane;1-phenylthio-3-methyl-Z-methyIcarbamyloximinobutane;l-benzylthio-3-methyl-2-methylcarbamyloximinobutane; and the like; aswell as analogous l-hydrocarbylthio-Z-methylcarbamyloximinobutanes suchas: l-methylthio-2-methylcarbamyloximinobutane;1-ethylthio-2-methylcarbamyloximinobutane;1-n-propylthio-2-methylcarbamyloximinobutane;1-isopropylthio-2-methylcarbamyloximinobutane;1-n-butylthio-2-methylcarbamyloximinobutane;l-tert.-butylthio-2-methylcarbamyloximinobutane;l-sec.-butylthio-Z-methylcarbamyloximinobutane;l-isobutylthio-2-methylcarbamyloximinobutane;l-vinylthio-2-methylcarbamyloximinobutane; l-( 2-propenylthio)-2-methylcarbamyloximinobutane; l-( 3-butenylthio)-2-methylcarbamyloximinobutane;l-ethynylthio-2-methylcarbamyloximinobutane;l-phenylthio-Z-methylcarbamyloximinobutane;l-benzylthio-2-methylcarbamyloximinobutane; and the like; as well asanalogous l-hydrocarbylthio-Z-methylcarbamyloximinopropanes such as:l-methylthio-2-methylcarbamyloximinopropane;l-ethylthio-2-methylcarbamyloximinopropane;l-n-propylthio-2-methylcarbamyloximinopropane;l-isopropylthio-Z-methylcarbamyloximinopropane;

1-n-butylthio-2-methylcarbamyloximinopropane;1-tert.-butylthio-2-methylcarbamyloximinopropane;l-sec.-butylthio-2-methylcarbamyloximinopropane;l-isobutylthio-Z-methylcarbamyloximinopropane;l-vinylthio-2-methylcarbamyloximinopropane;l-(2-propenylthi0)-2-methylcarbamyloximinopropane;l-(3-butenylthio)-2-methylcarbamyloximinopropane;l-ethynylthio-2-methylcarbamyloximinopropane;l-phenylthio-2-methylcarbamyloximinopropane;l-benzylthio-2-methylcarbamyloximinopropane;

the like; as well as carbamates of oximes of other straight or branchedmethyl-alkyl ketones where the methyl group is substituted with ahydrocarbylthio group such as:l-methylthio-2-methylcarbamyloximinopentane;l-methylthio-2-methylcarbamyloximinohexane;l-methylthio-4,4-dimethyl-2-methylcarbamyloximinopentane;l-methylthio-3,3-dimethylZ-methylcarbamyloximinopentane;l-methylthio-3,3-dimethyl-2-methylcarbamyloximinohexane; and the like.

Further examples of these compounds include those wherein the sulfidelinkage of the above compounds is replaced by an oxide linkage, asulfinyl linkage or a sulfonyl linkage as, for example:l-methoxy-3,3-dimethyl-2-methylcarbamyloximinobutane;l-ethoxy-3,3-dimethyl-2-methylcarbamyloximinobutane;l-(2-propenyloxy)-3,3-dimethyl-2-methylcarbamyloximinobutane;l-methoxy-3-methyl-2-methylcarbamyloximinobutane;l-ethoxy-3-methyl-2-methylcarbamyloximinobutane;l-(2-propenyloxy)-3-methyl-2-methylcarbamyloximinobutane;l-methoxy-Z-methylcarbamyloximinobutane;l-ethoxy-2-methylcarbamyloximinobutane;l-(2-propenyloxy)-2-methylcarbamyloximinobutane;l-methoxy-Z-methylcarbamyloximinopropane;l-ethoxy-2-methylcarbamyloximinopropane;l-(2-propenyloxy)-2-methylcarbamyloximinopropane; and:l-methylsulfinyl-3,3-dimethyl-2-methylcarbamyloximinobutane;l-ethylsulfinyl-3,3-dimethyl-2-methylcarbamyloximinobutane;l-(2-propenylsulfinyl)-3,3-dimethyl-2-methylcarbamyloximinobutane;l-methylsulfinyl-3-methyl-Z-methylcarbamyloximinobutane;l-ethylsulfinyl-3-methyl-2-methylc2irbamyloximinobutane;1-(2-propenylsulfinyl)-3-methyI-Z-methylcarbamyloximinobutane;l-methylsulfinyl-2-methylcarbamyloximinobutane;l-ethylsulfinyl-2-methylcarbamyloximinobutane;l-(2-propenylsulfinyl)-2-methylcarbamyloximinobutane;l-methylsulfinyl-Z-methylcarbamyloximinopropane;l-ethylsulfinyI-Z-methylcarbamyloximinopropane; 1-( 2-propenylsulfinyl)-2-methylcarbamyloximinopropane; and:1-methylsulfonyl-3,3-dimethyl-2-methylcarbamyloximinobutane;

and

l-ethylsulfonyl-3 ,3-dimethyl-2-methylcarbamyloximinobutane;

l-(2-propenylsulfonyl)-3,3-dimethyl-2-methylcarbamyloximinobutane;

l-methylsulfonyl-3-methyI-Z-methylcarbamyloximinobutane;

1-ethylsulfonyl-3-methyl-2-methylcarbamyloximinobutane;

1-( 2-propenylsulfonyl )-3-methyl-2-methylcarbamyloximinobutane;

l-methylsulfonyl-2-methylcarbamyloximinobutane;

l-ethylsulfonyl-2-methylcarbamyloximinobutane;

l-(2-propenylsulfonyl)-2-methylcarbamyloximinobutane;

1-methylsulfonyl-2-methylcarbamyloximinopropane;

l-ethylsulfonyl-2-methylcarbamyloximinopropane;

l-( Z-propenylsulfonyl Z-methylcarbamyloximinopropane;

and the like.

Further examples of these compounds include those wherein X is N;;.l-azido-2-methylcarbamyloximinopropane;1-azido-2-methylcarbamyloximinobutane;l-azido-2-methylcarbamyloximinopentane;l-azido-3-methyl-Z-methylcarbamyloximinobutane;l-azido-3-methyl-2-methylcarbamyloximinopentane;l-azido-4-methyl-2-methylcarbamyloximinopentane;l-azido-3,3-dimethyl-2-methylcarbamyloximinobutane;1-azido-3,3-dimethyl-2-methylcarbamyloximinopentane;l-azido-3,3-dimethyl-2-methylcarbamyloximinohexane;l-azido-4,4'dimethyl-2-methylcarbamyloximinopentane; and the like.

Additional examples of these compounds include those wherein twomemebers of the group R,, R and R are joined together to form a ring as,for example:

l-cyclopropyll -methylcarbamyloximinc-2- methylthioethane;

l-methylcarbamyloximino-1-( l-methylcyclopropyl)-2- methylthioethane;

Z-azidol -methylcarbamyloximinol l-methylcyclopr0pyl)ethane;

l-cyclobutyll -methylcarbamyloximino-Z- methylthioethane;

l-methylcarbamyloximino-1-( l-methylcyclobutyl)-2- methylthioethane;

2-azidol -methylcarbamyloximinol lmethylcyclobutyhethane;

l-cyclopentyl- 1 -methylcarbamyloximino-2- methylthioethane;

l-methylcarbamyloximinol l-methylcyclopentyl)-2- methylthioethane;

l-cyclohexyl-l-methylcarbamyloximino-2 methylthioethane;

l-methylcarbamyloximinol l-methylcyclohexyl)-2- methylthioethane;

2-azidol -methylcarbamyloximinol l-methylcy- .clohexyl)ethane; and thelike;

as well as compounds wherein R is X as, for example:

1,3-bis(methylthio)-3-methyI-Z-methylcarbamyloximinobutane;

3-methyl-Z-methylcarbamyloximinol -methylthio-3 nitrobutane;

3-methoxy-3-methyl-2-methylcarbamyloximinol methylthiobutane;

7 3-cyano-3-methyl-Z-methylcarbamyloximino-lmethylthiobutane;l-azido-3-methyl-2-methylcarbamyloximino-3- methylthiobutane;l-azido-3-methoxy-3-methyl-2-methylcarbamyloximinobutane;3-azido-3-methyl-2-methylcarbamyloximinol methylthiobutane;3-azido-l-methoxy-3-methyl-2-methylcarbamyloximinobutane;1-methoxy-3-methyl-2-methylcarbamyloximino-S- nitrobutane;l-methoxy-3-methyl-2-methylcarbamyloximino-3- methylthiobutane;3-cyano-l-methoxy-3-methyl-2-methylcarbamyloximinobutane; l,3-bis(methoxy )-3-methyl-2-methylcarbamyloximinobutane;l,3-bis(cyano)-3-methyl-Z-methylcarbamyloximinobutane;l-cyano-3-methyl-2-methylcarbamyloximino-3- methylthiobutane;l-cyano-3-methoxy-B-methyl-2-methylcarbamyloximinobutnne;l-nitro-3-mcthyl-2-methylcarbamyloximino-3- methylthiobutane;l-nitro-3-methoxy-3-methyl-Z-methylcarbamyloximinobutane;3-methyl-3-dimethylamino-2-methylcarbamyloximinol-methylthiobutane;l-methoxy-3-methyl-3-dimethylamino-Z-methylcarbamyloximinobutane;3-methyll-dimethylamino-Z-methylcarbamyloximino- 3-methylthiobutane;3-methoxy-3 -methyl- 1 -dimethylamino-2-methylcarbumyloximinobutane; andthe like;

as well as compounds wherein R is X as, for example:

l,l-bis(methylthio)-3,3-dirriethyL2-methylcarbamyloximinobutane;

l, 1 -bis( methoxy )-3 ,3-dimethyl-2-methylcarbamyloximinobutane;

l-methoxy-3 ,3-dimethyl-2-methylcarbamyloximinol methylthiobutane;

l, l -ethylenedithio-3,3-dimethyl-Z-methylcarbamyloximinobutane;

3,3-dimethyl-2-methylcarbamyloximinol ,1-( 1,2-

propylenedithio)-butane;

3,3-dimethyl-2-methylcarbamyloximino-1,l-(1,3-

propylenedithio)-butane;

l,1-ethylenedioxy-3.3-dimethyl-2-methylcarbamyloximinobutane;

3 ,3-dimethyl-2-methylcarbamyloximinol l 1,2-

propylenedioxy)-butane;

3,3-dimethyl-2-methylcarbamyloximino-l,l-(1,3-

propylenedioxy)-butane;

2,2-dimethyll -methylcarbamyloximinol 1,3-

oxathiolan-Z-yl)-propane;

2,2-dimethyl-l-methylcarbamyloximino-l-(1,3-

oxathian-2-yl)-propane;

2,2-dimethyll -methylcarbamyloximinol3-methyll,3-oxazolidin-2-yl)-propane;

2,2-dimethyl l -methylcarbamyloximinol 3- methyltetrahydro-l,3-oxazin-2-yl)-propane;

2,2-dimethyll -methylcarbamyloximinol 1,3-

dimethylimidazolidin-Z-yl)propane;

2,2-dimethyl-l-methylcarbamyloximino-1-(1,3-

dimethylpyrimidin-Z-yl)propane;

2,2-dimethyll -methylcarbamyloximinol 3- methylthiazolidin-2-yl)propane;2,2-dimethyl-l-methylcarbamyloximino-l-(3-methyltetrahydro-l.3-thiazin-2-yl)propane; and the like. Additionalexamples of these compounds include:3,3-dimethyl-2-methylcarbamyloximinol 2- methylthioethylthio)-butane;l-(Z-ethylthioethylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane;l-(2-methoxyethylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane;l-(Z-ethoxyethylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane;

- 3,3-dimethyl-2-methylcarbamyloximino-l-(2-methylsulfinylethylthio)butane;3,3-dimethyl-Z-methylcarbamyloximino-l-(2-methylsulfonylethylthio)butane;l-(Z-methoxyethoxy)-3,3-dimethyl-2-methylcarbamyloximinobutane;3,3-dimethyl-2-methylcarbamyloximino-l-(2- methylthioethoxy)-butane;3,3-dimethyl-Z-methylcarbamyloximino-l-(2- methylthiomethylthio)-butane;l-(2-methoxymethylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane;l-(Z-methoxymethoxy)-3,3-dimethyl-2-methylcarbamyloximinobutane;3,3-dimethyl-2-methylcarbamyloximino-l-(3,3,3-

trifluoropropylthio)butane;l-(3,3,3-trichloropropylthio)-3,3-dimethyl-2-methylcarbamyloximinobutane;l-'( 2-cyan oethylthio )-3 ,3-dimethyl-2-methylcarbamyloximinobutane;3,3-dimethyl-l-(Z-dimethylaminoethylthio)-2-methylcarbamyloximinobutane;3,3-dimethyl-2-methylcarbamyloximino-l-(2- phenethylthio)butane;3,3-dimethyl-Z-methylcarbamyloximino-l-(2-(2'- thenyl)ethylthio)-butane;3 ,3-dimethyl-2-methylcarbamyloximinol -propargylthiobutane; I l-cyano-3,3-dimethyl-2-methylcarbamyloximinobutane;

3 ,3-dimethyl-2-methylcarbamyloximinol -nitrobutane;

and the like.

Although the above compounds are, for purpose of illustration,N-methylcarbamates, the carbamate nitrogen of these compounds can beunsubstituted, as in the simple carbamates, or can be substituted with asingle alkyl. alkenyl or alkynyl substituent such as methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, allyl, propargyl, or the like,or can be substituted with two alkyl, alkenyl, or alkynyl groups, withthe groups being the same or different, to give, for example,N,N-dimethylcarbamyloximes; N,N-diethylcarbamyloximes; N-methyl-N-ethylcarbamyloximes; N,N-di-npropylcarbamyloximes; N-methyl-N-propylcarbamyloximes; N,N-diallylcarbamyloximes; N,N-dipropargyloximes;N-methyl-N- allylcarbamyloximes; N-methyl-N-propargylcarbamyloximes; andthe like.

It will be appreciated by those skilled in the art that the ketoximederivatives of this invention may exist in two geometric forms, the synand the anti, representing the cis and trans isomers around the oximedouble 9 10 bond. Both isomers and their mixtures are intended todimethylaniline. Reaction is carried out from about be included in thescope of this invention. -30 C to about 100 C, preferably at from aboutC These compounds can be prepared by one of several to about 50 C. Theresulting reaction mixture, a solumethods. One method involves reactionof an isocyation of the chloroformate in an inert organic solvent, natewith an oxime, as shown, for example, in the equacan be filtered orwashed with water to remove amine tion: I hydrochloride before it isused in the reaction shown in RNOHR R Noii a I t a I1 S I R I-C--( 1-X RNC0 R -C-C C-X R I R5 R3 R5 wherein R through R,; and X are as definedabove. The Equation (2).

oxime and isocyanate are reacted in an inert organic In the reactionshown in Equation (2), an amine is solvent from about 0 C to about 150C, preferably added to the chloroformate solution in the presence offrom about 20C to about 80C, and at a pressure from i an amine solventsuch as water, at temperatures beabout 1 to about atmospheres,preferably from tween about 40 C and about 80 C, preferably at about 1to about 3 atmospheres. Reaction pressure is about 0 C to about 40 C. Alarger than molar excess determined by reaction temperature,concentration of amine can be used so that the amine acts both as reandvapor pressure of the isocyanate. actant and as HCl acceptor andcomplete conversion of Any inert organic solvent used in the reactionshould chloroformate is obtained. Alternatively, a separate not containhydroxy, amino or other groups which will HCl acceptor, such as atertiary amine, can be used. react with the isocyanate function. Usefulinert solvents Liquid or solid carbamates produced by the above includealiphatic and aromatic hydrocarbons, such as methods can be recoveredfrom reaction mixtures by hexane, heptane, octane, benzene, toluene,xylene; conventional means. For example, they can be recovethers such asdiethyl ether, dipropyl ether, ethyl proered by removal of solvent andexcess amine or isocyapyl ethere; esters such as ethyl acetate, ethylpropionate by vacuum distillation. Although these products nate; ketonessuch as acetone, methyl ethyl ketone; and are obtained in very pureform, they can be further puchlorinated hydrocarbons such as methylenechloride, rified, if desired, by recrystallization, distillation,abperchloroethylene, and the like. sorption chromatography, or otherknown procedures. Preferably, reaction is carried out in the presence ofKetoxime intermediate useful in this invention can be from about 0.1 toabout 1.0% by weight, based on the prepared by well known proceduressuch as reaction of weight of reactants, of a tertiary amine catalystsuch as the ketone with hydroxylamine in aqueous ethanol. Hytriethylamine, N,N-dimethylaniline, or the like. drocarbyloxy or thio ketonescan be prepared by reac- The molar ratio of isocyanate to oxime can varyfrom tion of the haloketones with mercaptans or alcohols in about 0.111to about 10:1. An equimolar amount or the presence ofan acidacceptor,e.g., sodium alkoxide. slight excess of isocyanate is preferredto ensure com- Sulfinyl and sulfonyl linked compounds can be prepletereaction of the oxime. Reaction times can vary pared by oxidizing theappropriate sulfide linked comfrom a few minutes to several days.Usually reaction pound with sodium metaperiodate or acidic hydrogentimes of from about one-half to about six hours are sufperoxide,respectively. ficient. Although the compounds of this invention can beap- A second method for preparing these compounds inplied in undilutedform to the plant or other material volves reaction of an oxime withphosgene to obtain an being treated, it is usually desirable to applythese comoxime chloroformate which is then reacted with an pounds inadmixture with either solid or liquid inert, amine. This method isillustrated in Equations (1) and pesticidal adjuvants. For example, thecompounds can (2) below: be applied to plants for pesticidal purposes byspraying 9 1 1 I YOH 13 I'M l lOCC1 R (1) R ICC !--X coc1 R2--e--c :--x

0 0 II II R R NOCCl R R NOCN R (2) R ':g--t':-x HN R --'c'--- x I I 7 2I I R3 R5 R3 R5 wherein R through R, and X are as defined above. The theplants with aqueous or organic solvent dispersions method is carried outin two steps following the reacof the compounds. Choice of anappropriate solvent is tions shown in Equations (1) and (2). detereminedby factors such as concentration of active In the reaction shown inEquation (1), a solution of ingredient, the volatility required in thesolvent, cost of the oxime dissolved in an inert solvent such as diethylthe solvent, and nature of the material being treated. ether, is addedslowly to a solution of phosgene dis- Solvents, which can be employed ascarriers for these solved in an inert solvent in the presenceof an HClaccompounds, include hydrocarbons such as benzene,

ceptor such as a tertiary amine, e.g., N,N- toluene,xylene,kerosene,diesel oil, fuel oil, hydrocarbons, and naphthas; ketones suchas acetone, methyl ethyl ketone and cyclohexanone; chlorinatedhydrocarbons such as trichlorethylene, perchloroethylene; esters such asethyl acetate, amyl acetate and butyl acetate; ethers of ethylene glycolsuch as the monomethyl and monoalkyl ethers of diethylene glycol, themonoethyl ether of propylene glycol; alcohols such as ethanol,isopropanol, pentanols, and the like.

These compounds can also be applied to plants and other materials inconjunction with inert solid adjuvants or carriers such as talc,pyrophyllite, attapulgite, chalk, diatomaceous earth, koalinite,montmorillonite, other silicates, silica, lime, calcium carbonate,certain organic carriers such as walnut shell flour, wood flour, groundcorn cobs, and the like.

It is often desirable to use a surfactant (a surface active agent) inpesticidal compositions. An anionic, nonionic or cationic surfactant canbe used in the formulation of either solid or liquid compositions.Typical surfactants include alkyl sulfonates, alkylaryl sulfonates.alkyl sulfates, alkylamide sulfonates, alkylaryl polyether alcohols,fatty acid esters of polyhydric alcohols, ethylene oxide additionproducts of these esters; ethylene oxide addition products of long-chainmercaptans; sodium alkyl benzene sulfonates having 12 to 18 carbonatoms; ethylene oxide addition products of alkylphenols, such as phenolcondensed with moles of ethylene oxide; cetyl pyridinium chloride; soapssuch as sodium stearate and sodium oleate.

Solid and liquid formulations can be prepared by any suitable method.Solid active ingredients, in finely divided form, can be tumbledtogether with a finely divided solid carrier. Alternatively, the activeingredient in liquid forms such as solutions, dispersions, emulsions orsuspensions, can be admixed with the solid carrier in finely dividedform in amounts small enough to preserve the free-flowing property ofthe final dust compositions.

When solid formulations are used, in order to obtain a high degree ofcoverage with a minimum dosage, it is desirable that the formulation bein the form of a finely divided powder or dust sufficiently fine thatsubstantially all of the solids will pass through a Tyler sieve having amesh size between about 20 and about 200.

In dust formulations, the active ingredient can be present in an amountof 5 to 50% of the total weight. However, concentrations outside thisrange are operative and compositions containing from 1 to 99% of activeingredient by weight are contemplated wherein the remainder is carrierand/or any other desired additive or adjuvant. It may be advantageous toadd a small amount of surfactant, e.g., 0.5 to 1% by weight based on thetotal weight of the dust formulation.

For spray application, the active ingredient may be dissolved ordispersed in a liquid carrier, such as water or other suitable liquid.The active ingredient can be added in the form of a solution,suspension, dispersion or cmulsion in aqueous or nonaqueous medium.Desirably, 0.5 to 1.0% by weight of surfactant is present in the liquidcomposition.

For adjuvant purposes, any desired quantity of surfactant may beemployed, such as up to 250% by weight of the active ingredient. If thesurfactant is used only to impart wetting qualities to a spray solution,as little as 0.05% or less, by weight of the surfactant need be used.Larger quantities of surfactant are used because of biological behaviorof the surfactant rather than its wetting properties. Theseconsiderations are particularly important in the treatment of plants.The

active ingredient in liquid formulations often may not be more than 30%by weight of the total and may be 10% by weight of even as low as 0.01%by weight.

For systemic application, it may be desirable to apply the pesticide tothe soil in the form of granules of an inert material coated with orincorporating the active ingredient. Reasons for the use of pesticidalgranules include elimination of water during application, reduction ofdrift, penetration through vegetative coverage, easy handling, storage,and increased safety to handlers of the pesticides. Useful granule basematerials include attapulgite, montmorillonite, corn cobs, walnutshells, and expanded vermiculites. Depending on their physicalproperties, the pesticides are either directly sprayed on the preformedgranular base or are dissolved in a suitable solvent and then sprayedonto the granular base after which the solvent is removed byevaporation. Granule base materials are usually 60 to 14 US. sieve sizeparticles, although other size particles may also be used.

Terms pesticide and pesticidal as used herein are intended to refer tothe killing and/or control of insects, mites, nematodes, or the like. Itwill be appreciated that applications commonly referred to asinsecticidal, miticidal, nematocidal, or the like are contemplated inthe employment of these terms.

For a fuller understanding of the nature and objects of this invention,reference may be made to the following examples which are given toillustrate the invention and are not to be construed in a limitingsense. The infrared spectrum for each product described herein isconsistent with the assigned structure. All percentages, proportions,and quantities given in these examples are by weight unless otherwiseindicated. Likewise, all references to temperature are as C unlessotherwise indicated.

EXAMPLE 1 3,3-Dimethyl-l-tert.-butylthio-2-butanone (Compound 7569) To asolution of 5.8 g (0.25 m) of sodium metal in 175 ml of absolute ethanolis added, dropwise, 24.4 g (0.27 m) of 2-methyl-2-propanethiol. Thestirred solution is heated for 20 minutes, cooled, and treated in adropwise manner with 44.8 g (0.25 m) of lbromopinacolone, preparedaccording to the procedure ofJ. Am. Chem. Soc., 74, 4507 1952). Thisreaction mixture is heated at reflux for 20 minutes, cooled, and pouredonto 200 g of ice and water. After being saturated with sodium chloride,the mixture is extracted with four portions of ether. The combined etherextracts are dried over anhydrous magnesium sulfate, filtered, andstripped of solvent. Distillation of the residue through a shortVigreaux column gives the desired product. Properties of this, andsimilar compounds prepared by substantially the same procedure using theappropriate mercaptans and a-haloketones, are given in Tables 1 and 2.

EXAMPLE 2 3,3-Dimethyl-l-tert.-butylthio-2-butanone oxime (Compound7604) A solution of 27 g (0.14 m) of 3,3-dimethyl-l-tert.-butylthio-2-butanone, 19.5 g (0.28 m) of hydroxylamine hydrochloride and14.8 g (0.14 m) of anhydrous sodium carbonate in a mixture of 200 ml ofethanol and ml of water is heated at reflux for 19.5

hours. Stripping of volatiles on a rotary evaporator gives a slurrywhich is filtered to obtain the white solid oxime product. Properties ofthis and related compounds prepared by substantially the same procedureare given in Tables 3 and 4. Where the oxime product is a liquid,isolation is accomplished by ethyl acetate extraction of the residueleft after removal of the volatiles and subsequent stripping of thedried extract.

EXAMPLE 3 Carbamate Preparation Method A 3,3-dimethyl-2-methylcarbamyloximino-1-tert.- butylthiobutane (Compound7619) A solution of 4.7 g (0.023 m) of 3,3-dimethyl-l-tert.-butylthio-2-butanone oxime, 1.4 g (0.025 m) of methyl isocyanate, andthree drops of triethylamine in 35 ml of anhydrous ether is heated atreflux for 16.5 hours. Stripping of volatiles on a rotary evaporatorgives the desired product as a white solid. Properties of this andanalogous compounds prepared by substantially the same procedure aregiven in Tables 5 and 6.

EXAMPLE 4 Carbamate Preparation Method B 2-Carbamyloximino-3,3-dimethyll -methylthiobutane (Compound 7859) To a chilled solution of5.4 g (0.055 m) of phosgene in 50 ml of anhydrous ether is added,dropwise 6.1 g (0.05 m) of N,N-dimethylaniline followed by a solution of8.1 g (0.05 m) of 3,3-dimethyl-l-methylthio-2- butanone oxime in 50 mlof ether. The mixture is stirred for two hours, as it is allowed to cometo room temperature, and then filtered. The chilled filtrate is treatedover 15 minutes with ml (0.15 m) of 29% aqueous ammonia. After beingstirred for an additional minutes, the organic layer is separated,washed with water, and dried. Stripping of solvent from the organiclayer gives 10.1 g of a clear liquid residue which solidifies onstanding. Properties of this and analogous compounds prepared bysubstantially the same procedure are shown in Tables 5 and 6.

EXAMPLE 5 Carbamate Preparation Method C 3,3-Dimethyl-2-methylcarbamyloximino-l-(1- pyrro1idinyl)-butane (Compound7870) To a solution of 12.6 g of l-bromo-3,3-dimethy1-2-methylcarbamyloximinobutane in 100 ml of anhydrous ether is added,dropwise, 7.8 g (0. 11 m) of p'yrrolidine. The mixture is stirred atroom temperature for 1 hour and at reflux for 0.5 hour, then cooled andwashed with water. The ether solution is separated, dried, and strippedof solvent to give 11.8 g of amber oil which solidifes on standing to anamber solid, m. 43-46 C. Properties of this and analogous compoundsprepared by substantially the same procedure are shown in Tables 5 and6.

EXAMPLE 6 1-Bromo-3,3-dimethyl-2-butanone oxime (Compound A solution of69.5 g 1.0 m) of hydroxylamine hydrochloride in 100 ml of water ischilled in an ice bath as 90 g (0.5 m) ofl-bromo-3,3-dimethyl-2-butanone is added. After addition of 100 ml of95% ethanol, the mixture is stirred for 16 hours and allowed to warm toroom temperature. The resulting white slurry is filtered, and the solidis washed with water and dried to give 55 g of the desired compound, in.1 1 1-1 12 C.

Calcd. for C H NBrO: N, 7.2%; Br, 41.2% Found: N, 7.1%; Br, 42.4%

EXAMPLE 7 3,3-Dimethyl-l-nitro-2-butan one oxime (Compound 7668) To astirred solution of 18.2 g (0.26 m) of sodium nitrite in ml of dimethylsulfoxide is added, in portions, 29.0 g (0.15 m) ofl-bromo-3,3-dimethyl-2- butanone oxime. A mild exotherm results andexternal cooling is used to keep the temperature below 27 C. Additionalsolvent is added to maintain stirrability. After 20 hours stirring, themixture is poured onto ice and water to give a solid which is collectedon a filter. The 10 g of solid, in. 11 5-120 C, thus obtained isrecrystallized from a hot benzene-petroleum ether mixture to give 7 g ofwhite crystals, m. 124125C.

Calcd. for c -H gN- ogi C, 45.0%; H, 7.6%

Found: C, 45.2%; H, 7.8%

EXAMPLE 8 3,3-Dimethyl-2-methylcarbamyloximinol -methylsulfinylbutane(Compound 7804) A stirred mixture of 9.0 g (0.042 m) of sodiummetaperiodate in 60 ml of water and 25 ml of methanol is cooled to 0 Cas 8.7 g (0.04 m) of 3,3-dimethyl-2-methylcarbamyloximino-l-methylthiobutane is added in portions. Afterstirring at 0-l0 C for 18 hours, the mixture is allowed to warm to roomtemperature and stripped of volatiles on a rotary evaporator to give aresidue which is extracted with ethyl acetate. The dried extrace isstripped to leave 9 g (96%) of viscous yellow oil, the desired compound.

Calcd. for C H N O S: C, 46.1%; H, 7.7%

Found: C, 45.2%; H, 7.5%

EXAMPLE 9 2,Z-Dimethyl-3-methylcarbamyloximino-4-methylthiopentane(Compound 8071 To a solution of sodium thiomethoxide prepared from 4.1 g(0.18 gram atom) of sodium, 8.7 g (0.21 m) of methanethiol and 1 10 mlof ethanol is added 34.5 g (0.18 m) of 4-bromo-2,2-dimethyl-3-pentanoneover 25 minutes at 0 i 5 C. After being heated to 4045 C for 30 minutes,the solution is filtered, stripped of solvent and distilled to give 12 g(42%) of colorless liquid, b. 57 C/4.3 mm, n 1.4589.

Calcd. for C,,H ;OS: C, 59.9%; H, 10.1%

Found: C, 59.2%; H, 10.1%

This compound (7 g, 0.044 m) and 18 g (0.26 m) of hydroxylaminehydrochloride in ml of absolute ethanol containing 30 ml of pyridine areheated under reflux for 120 hours. Pouring the clear solution into icewater gives a solid which is collected and dried. This white solid, m.128-129 C, is the desired compound,2,Z-dimethyl-4-methylthio-3-pentanone oxime.

Calcd. for C H NOS: C, 54.8%; H, 9.8%; N, 8.0%

Found: C, 54.3%; H, 9.4%; N, 7.8%

A solution of 4.6 g (0.026 m) of this oxime, 1.7 g (0.029 m) of methylisocyanate, and three drops of triethylamine in 60 ml of benzene isheated under reflux for 17 hours. Stripping of volatiles gives 6.2 g ofsolid residue, m. 9394 C, which is the desired compound.

Calcd. for C H N O S: C, 51.7%; H, 8.7%; N,

12.1% Found: C, 51.6%; H, 8.5%; N, 12.1%

EXAMPLE 1 4,4-Dimethyl-3-methylcarbamyloximino-l-methylthiopentane(Compound 81 l l) A solution of sodium thiomethoxide, prepared from 5.8g (0.25 gram atom) of sodium, 135 g (0.28 m) of methanethiol, and 170 mlof absolute ethanol, is treated with 36.6 g (0.25 m) ofl-chloro-4,4-dimethyl- 3-pentanone at 3 to 8 C over 30 minutes. Afterbeing heated at 4045 C for 45 minutes, the mixture is filtered anddistilled to give 12 g of colorless liquid, b. 73 C/2 mm, n 1.4623.

Calc'd. for C,,H,,,OS: C, 59.9%; H, 10.1% I

Found: C, 60.1%; H, 10.0%

A solution of 22.5 g (0.14 m) of this ketone and 58.4 g (0.84 m) ofhydroxylamine hydrochloride in 525 ml of absolute ethanol and 105 ml ofpyridine is heated under reflux for 48 hours. Pouring the reactionmixture into ice water gives 17.8 g of a white solid, in. 84 C, which isthe desired 4,4-dimethyl-l-methylthio-3- pentanone oxime.

Calcd. for C H NOS: N, 8.0%

Found: N, 8.1%

Refluxing a solution of 5.3 g (0.03 m) of this oxime, 1.9 g (0.033 m) ofmethyl isocyanate, and three drops of triethylamine in 50 ml ofanhydrous ether gives, after stripping of volatiles, 7.6 g of whitesolid residue, m. 5658 C, which is the desired compound.

Calcd. for C,,,H ,,N O S: C, 51.7%; H, 8.7%; N,

12.1% Found: C, 51.6%; H, 8.5%; N, 12.5%

EXAMPLE 11 l -Cyc1ohexyl-1-methylcarbamyloximino-Z- methylthioethane(Compound 8169) To a solution of 10.8 g (0.47 m) of sodium in 330 ml ofabsolute ethanol is added 25 g (0.52 m) of methanethiol followed by 76 g(0.47 m) of chloroacetylcyclohexane. Both additions are carried out atabout 0 C. After being heated at 4045 C for 1 hour, the reaction mixtureis filtered, stripped, and distilled to give 29.8 g of colorless liquid,b. 88-89 C/0.6-1.3 mm, n 1.4970, the desired ketone.

Calc'd. for C H OS: C, 62.7%; H, 9.4%

Found: C, 63.0%; H, 8.6%

A solution of 26 g (0.15 m) of the l-methylthioacetylcyclohexane, 21 g(0.3 m) of hydroxylamine hydrochloride, and 16 g (0.15 m) of anhydroussodium carbonate in 155 ml of 95% ethanol and 104 ml of water is heatedunder reflux for 41 hours. Stripping of volatiles gives 18 g of solid,m. 6364 C, which is the desired oxime.

Calcd. for C,,H, NOS: C, 57.7%; H, 9.2%; N, 7.5%

Found: C, 57.5%; H, 9.0%; N, 7.4%

Heating a solution of 5.6 g (0.03 m) of this oxime, 1.9 g (0.033 m) ofmethyl isocyanate, and three drops of triethylamine in 50 ml of absoluteether at reflux for 17 hours gives, after removal of volatiles, 7.3 g ofsolid which is recrystallized from ethanol-water to obtain a whitesolid, m. 70-7l C, which is the desired com- 1 pound.

Calcd. for C H N O S: C, 54.1%; H, 8.3%; N,

11.5% Found: C, 54.2%; H, 8.3%; N, 11.7%

EXAMPLE 12 l Methylcarbamyloximinol-( l-methylcyclohexyl)-2-methylthioethane (Compound 8179) 1 Methylthioacetyl 1 -methylcyclohexaneis prepared by treating a solution of sodium thiomethoxide [from 3 g(013 gram atom) of sodium, 6.7 g (0.14 m) of methanethiol, and ml ofabsolute ethanol] with 22.5 g (0.13 m) ofl-chloroacetyl-lmethylcyclohexane over 20 minutes at 4-9 C. After beingheated at 4045" C for 1 hour, the reaction mixture is filtered anddistilled to give 7 g of colorless liquid, b. 8687 C/0.8 mm, n 1.4954.

Calcd. for C H OS: C, 64.5%; H, 9.7%

Found: C, 64.0%; H, 9.6%

This ketone is converted to the oxime by heating a solution of5 g (0.027m) of ketone, 3.8 g (0.054 m) of hydroxylamine hydrochloride, and 3 g(0.027 m) of anhydrous sodium carbonate in 30 ml of 95% ethanol and 26ml of water for 95 hours. The resulting solution is stripped ofvolatiles, to give a two-layer liquid residue, which is extracted withethyl acetate. The organic layer is dried, filtered, and stripped togive 3.4 g of amber liquid, n 1.5164.

Calcd. for C H NOS: C, 59.7%; H, 9.5%; N, 7.0%

Found: C, 59.8%; H, 9.5%; N, 7.0%

A solution of 2.2 g (0.011 m) of this oxime, 0.7 g (0.012 m) of methylisocyanate, and three drops of triethylamine in 25 ml of anhydrous etheris heated at reflux for 16 hours. Stripping of volatiles gives 3.5 g ofamber viscous liquid, n 1.5200, which is the desired compound.

Calcd. for C H N O S: C, 55.8%; H, 8.6%

Found: C, 55.7%; H, 8.6%

EXAMPLE l3 1-( l-Adamantyl)- 1 -methylcarbamyloximino-2-methylthioethane (Compound 8191 A solution of 4 g (0.018 m) ofl-methylthioacetyladamantane, 2.5 g (0.036 m) of hydroxylaminehydrochloride, and 1.9 g (0.018 m) of anhydrous sodium carbonate in 20m1 of 95% ethanol and 18 ml of water is heated under reflux for 29hours. Stripping of volatiles gives a slurry which is filtered to obtain4.2 g of white solid oxime, m. l00-l03 C.

Calcd. for,C H,NOS: C, 65.2%; H, 8.8%; N, 5.9%

Found: C, 65.5%; H, 8.8%; N, 5.6%

A solution of 3 g (0.013 m) of this oxime, 0.8 g

(0.014 m) of methyl isocyanate, and three drops of triethylamine in 50ml of anhydrous ether is heated under reflux for 17 hours. Stripping ofvolatiles gives 3.9 g of white solid, m. 99-100 C, which is the desiredcompound.

Calcd. for C H N O S: C, 60.8%; H, 8.2%; N, 9.5% Found: C, 60.2%; H,8.1%; N, 9.5%

EXAMPLE 14 l-Chloro-4,4-dimethyl-2-methylcarbamyloximinopentane(Compound 8108) To a chilled, stirred mixture of 20.2 g (0.29 m) ofhydroxylamine hydrochloride in 30 ml of water is added 21.5 g (0.145 m)of l-chloro-4,4-dimethyl-2- pentanone followed by 30 ml of 95% ethanol.The cooled mixture is stirred for six hours, allowed to stand overnight,and stripped of volatiles to obtain a residue which extracted with ethylacetate. This extract is dried, stripped, and distilled to yield acolorless liquid, b. 76-77 C/l.3 mm, 11, 1.4672. which is the desiredoxime.

Calcd. for C H C1NO:C, 51.4%; H, 8.6%; N, 8.6%

Found: C, 50.7%; H. 8.4%; N. 8.1% 1

A solution of 7 g (0.043 m) of the above oxime. 2.7. g (0.047 m) ofmethyl isocyanate, and three drops of triethylamine in 50 ml ofanhydrous ether is heated under reflux for 17 hours. Stripping ofvolatiles gives the desired carbamate as a colorless, viscous liquid, n1.4802.

Calcd. for C H C1N O N, 12.7%

18 having a reactive halogen radical Y, such as chlorine or bromine isreacted with HX having an X radical, as defined above. in the presenceof an HY acceptor. Table 6 shows other compositions prepared by MethodC.

TABLE 1 KETON ES FOUl'lClI N, 12.8% Compound EXAMPLE 14A Number ChemicalName 3,3-Dimethy1-2-methylcarbamyloximino-1'methy1su1- Z Z- 1 b g' 2 igqiihpfi nonil I 1 b -C2ll' omet oxymet y! lO- lmet UlilllOflEfonyloxybumne (Compound 9350) 7533 1-methy|thio-2-propanone 75573-methy1-3-methylthio-Z-butanone A solution of 7.5 g (0.04 in) of1-hydroxy-3,3- 755s 1-isopropy|thio-3,3dimethyl-2-butanonedimethy1-2-methylcarbamyloximinobutane and 5.0 g 20 75693,3-dimethyl-1-tert.:butylthio-Z-butanone (0.044 m) of methanesulfonylchloride in 50 ml of benzene is treated dropwise with 4.6 g (0.044 m) oftrieth- 77, 7 a 1 ylamine with cooling to keep the temperature below7665 3345111611111-l-P11eny1thl0-3-hulflflm1e 35C Af h h d h d 76671,3-bis(methylthio)-3-methyl'2-butanone tert e a 1t1on,t e stirremixture 1s eate 7765 33 dimethy| 1 phenoxy z bumnone at 35 C for twohours and then washed with aqueous 25 Z32 y l-l-progmnone .73-methyl-1-met ylthio-Z- utanone sodium bicarbonate and with water. Theorgamclayer 7838 33 dimethyl I n propy|thio 2 bumnone is dried overmagnesium sulfate, filtered, and stripped 78601-ethy1thi0-3.3-dimethyl-2-butanone c 7900 l-methylthio-Z-butanone ofYOldIllfiSjO give 6.7 g (63 /c) of amber. viscous liquid 7909lldimethYlLmethyhhioamemnone resldue, "n 7965 4,4-dimethyl-lmethylthio-3-pentanone Calcd. for C H N O S: C, 40.6%; H, 6.8%; N, 308059 y p S17 8126 1-methy1-1-(methylthioacetyl)-cyclohexane l 8127methylthioacetylcyclohexane Found: C, 41.2%; H, 6.8%; N, 10.5% 8373methylthioacetylcyclopropane 8504 4,4-dimethyl-1-methylthio-2-pentanoneExample 5 describes Method C for preparlng these 9011 4 methy| Imethy|thi0 3 pemanone compositions whereln a compound of the formula9061 l-methylthio-Z-pentanone 92741,1-bis(methylthio)-3,3-dimethy1-2-butanone 9 9275 1-(2-ethylthioethylthio )-3,3-dimethyl-2-butanone R 9278 1-methoxy-3.3-dimethy1-2-butanone R1 I f-OCK R4 93801-(3,3,3-trifluoropropylthio)-3.3-dimethyl-2-butanone l 7 I 93823,3,3-trich1oropropyl )-3 .3-dimethyl-2-butanone R -CC C Y 93833.3-dimethyl- 1 2-pheny1ethy1thio )-2-butanone rge is 9385 3,3-dimethy1- l -propargy1thio-2-butanone swig R 0 I! R --CC CH XCompound Boiling Range Refractive Percent Analysis Number R R R;, X inClmm Hg Index/C Yield Calculated Found 7218 CH CH, 011,- cH .,s 73/931.4650/24 62 7443 CH;, CH;, CH CH;,OCOCH S 94/08 1.4720/24 64 C 52.9 C52.6 H 7.9 H 7.5 7533 H H- H CH;,S 63-4/29 1.4691/24 45 C 46.1 C 46.9 H7. H 7.9 7557 CH CH;, CH;,S H- 48/8.1 1.4625/24 57 C 54.5 C 54.2 H 9.2 H9.2 7558 CH;, CH;. CH; (CH,-,) CHS 96/89 1.4568/24 68 C 62.0 C 61.8 H10.4 H 10.2 7569 CH CH;, CH;. (CH;;);,CS- 84-92/9.8 1.4595/24 67 C 63.8C 63.6 H 10.7 H 10.6 757 1 CH;, CH;, CH;; (CH;.)- CHCH S 101/981.4592/24 62 C 63.8 C 63.1 H 10.7 H 10.8 7573 CH;.- CH CH;, CH =CHCH S589/1.2 1.4762/24 24 C 62.7 C 62.8 H 9.4 H 9.1 7637 CH;,- CH;, CH C H CHS 104.5-106/ 1.5306/24 57 C 70.2 C 70.9 0.5-0.6 H 8.2 H 9.0 7665 CH,-,CH;, CH;, C H,-,S- 102/05 1.5425/24 38 C 69.2 C 70.0 H 7.7 H 7.7 7667CH;. CH;; CH -,S CH S 91-5/39 1.5138/23 56 C 47.2 C 46.8 H 7.9 H 7.87765"" cH, cH,, cH,, c,,1-1 -,o l06-8/1.8 1.5036/23 72 7807"" CH -,S- HH CH S IDS/9.5 1.5302/24 27 7837 01-1,- CH,, H- c1-1,.s* 61/8 48 c 54.6C 54.9 H 9.1 H 9.7

The compounds are evaluated for biological activity against thefollowing representative pests: Mexican bean bettle (Epilaclinavarivestis), Southern army worm (Prodenia eridania), housefly (Muscadomestica), bean aphid (Aphisfabue). and red spider mite (Terranyclmss1). The last two pests are treated both by contact and systemicapplication.

For purposes of comparison, results obtained with known Compound 7472.Compound 7577, and al- This test determines the acaricidal iactivity ofthe compound being tested against the red spider mite. Tetranyc/ms $1).Stock formulations containing 500 ppm of each test chemical are preparedby the procedure described in Example 15 and are used in both the soildrench and spray treatments. The stock culture of mites is maintained onScarlet runner bean foliage. Approximately l8 to 24 hours beforetesting, mites are transferred to the primary leaves of two Lima beandicarb are included in the test results. Each test com- 10 plants (var.Sieva) grown in 2% inch pots.

pound is rated using the following scale:

Contact Activity Systemic Activity The spray and systemic applicationmethods described in Example are used to apply the test formulations tothe infested plants and soil. After three days, two of the four leavestreated are examined and mortal- Bean Aphid Spray and Systemic Test Thistest determines the insecticidal activity of the compound being testedagainst the bean aphid Aphisfabae. Stock formulations containing 500 ppmof each test chemical are prepared using 0.05 g of the test chemical (or0.05 ml if a liquid), 4.0 ml acetone containing 0.25% (V/V) TritonX-l55, and 96.0 ml deionized water and are used in both soil drench andspray treatments. The stock formulations are diluted to obtain theappropriate lower concentrations maintaining the concentration level ofall adjuvants. The bean aphid is cultured on nasturtium plants (var.Tall Single), no attempt being made to select insects of a given age inthese tests. Single nasturtium test plants growing in soil in individual2% inch fiber pots are then infested with populations of 100 to 200aphids.

In the spray application, 50 ml of stock or diluted formulation isuniformly sprayed onto the plants. in the. systemic application, 1 1.2ml of stock or diluted formulation is applied to the soil containing theplant. A dosage of 11.2 ml of formulation containing 500 ppm of testchemical is equivalent to a dosage of the test chemical of 16 pounds peracre.

The plant test units under fluorescent lights are given bottom wateringfor the duration of the test. Percentage mortality is determined threedays after treatment. Results of this test are shown in Table 7 asA(aphid contact spray) and AS (aphid systemic soil drench).

EXAMPLE 16 Red Spider Mite Sptay and Systemic Test ity is determined.Should a compound be an effective miticide, the other two leaves areavailable to obtain information on the residual activity of theformulation. Results of this test are shown in Table 7 as M (mitecontact spray test) and MS (mite systemic soil drench test).

EXAMPLE l7 Housefly Spray Test This test determines the insecticidalactivity of the compound being tested against adult houseflies, Muscadomestica. Stock formulations containing 500 ppm of each test chemicalare prepared using the procedure described in Example 15 and are dilutedto obtain the appropriate lower concentrations.

Ten adult flies are placed in a cylindrical screen cage 1%. by 4 inchesfabricated from 20-mesh stainless steel screening and are sprayed with50 ml of the stock or diluted formulation. The flies are suplied foodand drink from a dextrose solution by draping a paper wick over theoutside of the screen cylinder and are able to feed and drink adlibitum. Percent mortality obtained is determined three days aftertreatment. Results of this test are shown in Table 7 as HF (houseflyspray test).

EXAMPLE is Southern Army Worm Spray Test Paired fully expanded primaryleaves excited from I Scarlet runner bean plants are maintained inplastic tubes containing water and sprayed with the test formulationprepared as described in ExamplelS. After the spray deposit on theleaves is dry, the paired leaves are separated. One leaf is placed onto1.5 percent water agar and infested with 10 newly hatched Southern armyworm larvae. The covered test receptacle is held at 72.

F for three days and then the percent mortality is determined. Resultsof this test are shown in Table 7 as AW (Southern army worm spray test).

EXAMPLE 19 e Mexican Bean Beetle Leaf Spray'Test This test determinesthe insecticidal activity of the compound being tested against theMexican bean beetle (Epilaclzna rarirestis). The test procedure is thesame as that described for the Southern army worm in Example 18 with theexception that one-day old larvae of the Mexican bean beetle instead ofnewly hatched Southern army worm larvae are used.

These tests are held at 72 F for three days when mortality and feedinginhibition are determined. The feeding inhibition is an indication ofthe repellent properties of the test material. Results of this test areshown in Table 7 as BB (Mexican bean beetle leaf spray test).

TABLE 7 Compound Number 7268 7472 7503 7577 7603 7718 7797 7799 78047859 7862 7867 7871 7897 79 l 6 7934 7960 799] 807] 81 l l 8465 85198520 8868 8997 9026 9057 9058 aldicarb BB Mexican hcan beetle AWSouthcrn army worm HF houscfl M mite contact A aphid contact MS mitesystemic 7 AS aphid systemic The high insecticidal and miticidalactivity of Compound 7268 is further demonstrated by the results ofspecial tests described below.

EXAMPLE 20 Systemic Test of Compound 7268 Against Lygus Bug and SpottedCucumber Beetle The techniques used are essentiallythesame for thesystemic tests described above in Example-l 5. The test compound isCompound 7268. There is one Sieva bean plant per pot and five adultinsects are caged on each plant. One plant is used for each testspecies. The checks showed no mortality during the tests.

The test organism is a strain of Southern corn rootworm (Diabroticaundecimpunctala howardi) resistant to chlorinated hydrocarboninsecticides and the test compound is Compound 7268. Duplicate samplesof sand-soil mixtures are treated with appropriate volumes of testformulation to give the desired dosages. The sand-soil samples are incovered paper cups, and several hours after drenching, all cups aregiven a thorough shaking to-provide complete and uniform mixing of thechemical throughout the soil. One day after treatment, two cornseedlings and five rootworms are placed into each cup and the lidsreplaced. Five days later, mortality is determined. The results aregiven below:

The techniques used are essentially the same as for the systemic testsdescribed above in Example 15. The test plants are cucumber seedlings;the test compound is Compound 7268; and the pest is the melon aphid(Aplzis gosyppi).

Dosage. lb/A 0.5 0.25 0.125 0.062 Control 100 100 100 EXAMPLE 23Residual Systemic Activity of Compound 7268 Against Mexican BeanBeetleLarvae Three furrows are opened in soil contained in 8 inch X 10inch X 3 inch fiber pans and 12 Pinto bean seeds day-old bean beetlelarvae. Mortality is determined three days later.

Weeks After 7? Mortality at Indicated Dosage. lh/A Treatment l 0.5 0.2.5Check 3 100 100 100 7 I00 100 I00 l0 I0 95 100 I00 0 l l 95 70 95 0EXAMPLE 24 Root-knot Nematocide Test This test is an evaluation of theeffectiveness of the compound being tested against infection byroot-knot nematodes (Meloidogyne spp.

Composted greenhouse soil, diluted by one-third with clean washed sand.is infested with about two grams of knotted or galled tomato roots perpot. Treatment is accomplished by applying 25 ml of the formulatedcompound onto the infested soil. The test formulation contains 0.056 gof Compound 7960, 1.0 ml stock emulsifier solution (0.25% Triton X-l55in acetone by volume), and 24.0 ml deionized water, giving aconcentration of 2240 ppm. Lower concentrations are achieved bydilution.

After treatment with the test formulation, the soil, inoculum, andformulation are thoroughly mixed, returned to the pot, and the mixtureincubated for seven days at 20 C and constant moisture. Afterincubation, two seedlings of Rutgers tomato transplants and three gardennasturtium (Nasturtium spp.) seeds are set in each pot. Roots areremoved from the soil after three weeks of growth and rated for gall(root-knot nematode infection) formation. Nasturtium roots are evaluatedonly when necrosis of the tomato host has occurred. A rating ofinfection from O to 10 is recorded:

no galls or complete control, and 10 heavily galled roots comparable tocontrols. Each of the root systems is rated separately and the averageis multiplied by 10 and subtracted from 100 to give percent nematodecontrol. Results of the test are shown below:

Compound Percent Control at Indicated Dosage. lb/A Number 8 4 2 1 0.5

7960 100 100 100 I 00 97 8423 I00 90 60 8997 100 100 0 9026 90 7O 60 3034 fined by the appended claims.

What is claimed is: l. A composition of matter having the structuralformula:

0 ll R6 R, N ocn H ll R t 2 C C C X l5 where:

a. R is hydrogen or lower alkyl; b. R; R is lower alkyl with the provisothat R and R may be connected to form a cycloalkyl ring of 90 not morethan 6 carbon atoms;

c. R R is hydrogen, lower alkyl or lower alkenyl;

d. X is SR S(O)R or 50 R and,

e. R is hydrogen, lower alkyl, lower alkenyl, lower alkynyl, or aryl,

5 2. A composition of matter of claim 1 selected from the groupconsisting of:

3,3-dimethyl-2-methylcarbamyloximino-lmethylthiobutane;

3,3-dimethyl-2-methylcarbamyloximino-l-methylsulfinylbutane;3.3-dimethyl-2-methylcarbamyloximinol methylthiohexane;2-carbamyloximino-3,3-dimethyl-l-methylthiobutane;3-methyl-2-methylcarbamyloximino l methylthiobutane;l-ethylthio-3,3-dimethyl-Z-methylcarbamyloximinobutane; v l-cyclopropyll-methylcarbamyloximinc-2- methylthioethane;

40 3,3-dimethyl-2-methylcarbamyloximino-l-methylthiopentane;

3,3-dimethyl-2-methylcarbamyloximino-l-methylsulfonylbutane,

2-ethylcarbamyloximino-3,3-dimethyl-lmethylthiobutane2-allylcarbamyloximino-3,3-dimethyl methylthiobutanel-allythio-3,3-dimethyl-2-methylcarbamyloximinobutane 503,3-dimethyl-Z-methylcarbamyloximino- 1 -npropylthiobutane.

3. The composition of matter of claim 1 wherein the composition is3,3-dimethyl-2- methylcarbamyloximino-l-methylthiobutane.

4. The composition of matter of claim 1 wherein the composition is3,3-dimethyl-2- methylcarbamyloximinol-methylsulfinylbutane.

5. The composition of matter of claim 1 wherein the composition is3,3-dimethyl-2- methylcarbamyloximinol -methylthiopentane.

6. The composition of matter of claim 1 wherein the composition is3,3-dimethyl-2- methylcarbamyloximinol -methylsulfonylbutane.

1. A COMPOSITION OF MATTER HAVING THE STRUCTURAL FORMULA:
 2. Acomposition of matter of claim 1 selected from the group consisting of:3,3-dimethyl-2-methylcarbamyloximino-1-methylthiobutane;3,3-dimethyl-2-methylcarbamyloximino-1-methylsulfinylbutane;3,3-dimethyl-2-methylcarbamyloximino-1-methylthiohexane;2-carbamyloximino-3,3-dimethyl-1-methylthiobutane;3-methyl-2-methylcarbamyloximino-1-methylthiobutane;1-ethylthio-3,3-dimethyl-2-methylcarbamyloximinobutane;1-cyclopropyl-1-methylcarbamyloximino-2-methylthioethane;3,3-dimethyl-2-methylcarbamylOximino-1-methylthiopentane;3,3-dimethyl-2-methylcarbamyloximino-1-methylsulfonylbutane,2-ethylcarbamyloximino-3,3-dimethyl-1-methylthiobutane2-allylcarbamyloximino-3,3-dimethyl -1-methylthiobutane1-allythio-3,3-dimethyl-2-methylcarbamyloximinobutane3,3-dimethyl-2-methylcarbamyloximino-1-n-propylthiobutane.
 3. Thecomposition of matter of claim 1 wherein the composition is3,3-dimethyl-2-methylcarbamyloximino-1-methylthiobutane.
 4. Thecomposition of matter of claim 1 wherein the composition is3,3-dimethyl-2-methylcarbamyloximino-1-methylsulfinylbutane.
 5. Thecomposition of matter of claim 1 wherein the composition is3,3-dimethyl-2-methylcarbamyloximino-1-methylthiopentane.
 6. Thecomposition of matter of claim 1 wherein the composition is3,3-dimethyl-2-methylcarbamyloximino-1-methylsulfonylbutane.